As mascaras, eyeliners, and other make-up cosmetics, there have conventionally been known, roughly devided, emulsion types, film types, emulsion-film types, oil types, oil-emulsion types, and oil-film types. A brief explanation will be given of these various types below.
First, the emulsion type is an oil-in-water type emulsion comprised mainly of a solid, semi-solid, or liquid oil and an aqueous system. Cosmetics of this type easily are detached due to water, perspiration, tears, etc. Further, mascara etc. runs into the sebum on the face and the oil components of the emulsion or other cosmetics and thus tends to stain the area around the eyes with lapse of time.
Next, regarding the film type, use has been made of polymer emulsions obtained by emulsion polymerization using natural latex or water-soluble polymers or emulsifiers as the film forming agent, but these polymer materials themselves are poor in water resistance, and therefore, could not give sufficient water resistance as a cosmetic.
An attempt was made to solve these problems with a solid, semi-solid oil--water--polymer emulsion type emulsion-film type of cosmetic as disclosed in Japanese Unexamined Patent Publication (Kokai) No. 50-125043. However, while it was possible to delay the penetration of water by formulating wax thereto, no consideration was given to the water resistance of the polymer emulsion per se so that the solution was not necessarily complete.
The oil type is comprised of a solid, semi-solid, or liquid oil component--volatile branched hydrocarbon system, so is excellent in water resistance, but is completely poor in oil resistance and dryness.
The oil-emulsion type is a solid, semi-solid, or liquid oil component--volatile branched hydrocarbon--aqueous water-in-oil type emulsion. This is excellent in water resistance and dryness, but in general the composition is obtained by dissolving solid paraffin, wax, or a lanolin derivative in a volatile branched hydrocarbon, then dispersing various types of pigment powders therein, so especially in the case of mascaras and eyeliners, even after drying, the mascara or eyeliner dissolves into the sebum or oil component of other cosmetics present there due to blinking etc., so the pigment falls off from the film and adheres to the lower eyelids (secondary adhesion) or stains the area around the eyes, that is, the oil resistance is poor.
An attempt was made to solve this problem by the oil-film type obtained by mixing an oil-soluble film agent as disclosed in Japanese Unexamined Patent Publication (Kokai) No. 52-27695. This is an oil-in-water-in-oil type (O/W/O) comprised of a solid, semi-solid, liquid oil component--volatile branched hydrocarbon--synthetic resin emulsion system. Since both the oil and water are used as volatile solvents and each include solid components and film agents, the cosmetic staying power is improved. Since the pigments are included in the external phase, however, the pigments redisperse due to the sebum and the oil component contained in the cosmetics, so it is not possible to prevent detachment or to completely eliminate adhesion or running, as disclosed in, for example, JP-A-58-180412.
Recently, further, the technology for a make-up cosmetic using an organic silicone resin as a film agent has been developed (Japanese Unexamined Patent Publication (Kokai) Nos. 61-18708, 61-65809, and 61-161211). The following characteristics are obtained when an organic silicone resin is used, so this is useful:
(1) A strong film is formed after drying. PA0 (2) After drying, there is complete insolubility in the water or film component, cream, emulsion, cosmetic base, or other oil components used in cosmetics. PA0 (3) There is, however, solubility in the volatile oil component used in make-up removers etc.
In the above inventions, however, since an organic silicone resin is formulated in the same phase as the phase in which the pigment or solid, semisolid, or liquid oil component, oil-soluble resin, etc. are dispersed or dissolved, after drying, the organic silicone resin becomes a discontinuous film due to the pigment. Accordingly, the film swells due to the liquid oil component and physical stimulus causes detachment or running of the pigment. The above was the prior art for make-up cosmetics such as eyeliners and mascaras.
In addition, one technology for improving the cosmetic staying power of make-up cosmetics was a hydrophobic treatment with powder. The main type of this was treatment with silicone which is superior in water repellency and oil repellency (see U.S. Pat. No. 4988502, Japanese Examined Patent Publication (Kokoku) No. 41-9890, Japanese Examined Patent Publication (Kokoku) No. 45-2915, Japanese Examined Patent Publication (Kokoku) No. 45-18999, Japanese Unexamined Patent Publication (Kokai) No. 54-56083, Japanese Unexamined Patent Publication (Kokai) No. 61-189211, and Japanese Examined Patent Publication (Kokoku) No. 2-191211). The development of these silicone treatment powders has, in particular, improved the cosmetic staying power of foundations, spot covers, etc., but since the pigment per se is exposed to the external environment, while there is the effect of shedding water, the cosmetic washes away with a large amount of water or oil or easily comes off with physical friction to thus stain the collars of shirts.
Accordingly, the object of the present invention is to provide a water-in-oil type make-up cosmetic composition which is superior in water resistance, perspiration resistance, sebum resistance, and oil resistance.
In accordance with the present invention, there is provided a water-in-oil type make-up cosmetic composition which includes 1 to 54% by weight of an oil-soluble resin in an external phase and includes a coloring material in an inner phase.
The present inventors engaged in intensive studies in consideration of these circumstances and as a result completed the make-up cosmetic of the present invention, which (1) can guard against the pigment directly contacting the external environment by mixing the pigment or other coloring agent into the inner phase and (2) can maintain continuity of the film after drying by mixing an oil-soluble resin, in particular, an organic silicone resin, in the external phase, whereby the cosmetic staying power can be strikingly improved, there is no running at all into water or oil, and the cosmetic can be removed by quickly dissolving in a volatile oil component of a remover or the like.
The constitution of the present invention will be explained in detail below.
First, the oil phase of the water-in-oil type makeup cosmetic composition of the present invention is mainly composed of an oil-soluble resin and a volatile oil component.
As the oil-soluble resin used in the present invention, mention may be made of fluoro resins, silicone resins, aromatic hydrocarbon resins, terpene resins, polybutene, polyisoprene, alkyd resins, and PVP modified polymers.
The fluoro resins include acrylic resins containing perfluoroalkyl groups, methacrylic resins containing perfluoroalkyl groups, and other resins having perfluoroalkyl groups as a pendant group in the main chain of a hydrocarbon, resins where the main chain per se is a fluorocarbon, such as polyfluorovinylidene, and resins having both a hydrocarbon portion and a fluorocarbon portion at the main chain obtained by radical copolymerization of fluoroethylene and a hydrocarbon type vinyl ether, but the resins are not limited to the above-mentioned compounds so long as the resins dissolve in a volatile solvent. For example, mention may be made of Fluorocoat EC-104, Fluorocoat EC-106, Fluorocoat EC-200, Fluorocoat EC-300 (made by Asahi Glass Co., Ltd.) etc. which are available on the market in a form dissolved in a volatile solvent.
The silicone resin is a copolymer composed of structural units of SiO.sub.2, RSiO.sub.3/2, R.sub.2 SiO, or other units of the general formula R.sub.n SiO.sub.4-n/2 (wherein, R is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a phenyl group, and n is a number of 1.0 to 1.8) or copolymers obtained by terminating the end with R.sub.3 SiO.sub.1/2 (wherein R is the same as mentioned above). More specifically, mention may be made of KR-285, KR-278, KR-114, etc. of Shin-Etsu Chemical Co., Ltd. Use may be made of silicone rubber of a polymerization degree n of dimethylpoly-siloxane of 5000 to 8000.
Further, as the aromatic hydrocarbon resin, mention may be made of Nisseki Neopolymer T, 120, 140, etc. of Nihon Sekiyu Co., Ltd. As a terpene resin, mention may be made of Quintone A-100, B-170, C-100, etc. of Nippon Zeon Co., Ltd. As the polybutene, mention may be made of Polybutene 200 etc. of Idemitsu Sekiyu Co., Ltd. As the polyisoprene, mention may be made of EscoRez 1071, 1103, etc. of Exxon Corp. As the alkyd resin, mention may be made of Veccozol EL8011, Solid Veccozol No. 31, No. 96, etc. of Dainippon Ink and Chemicals Co., Ltd. As the PVP modified polymer, mention may be made of Ganex V-216, V-220, etc. of Gokyo Sangyosha Co., Ltd.
Among these resins, when use is made of an organic silicone resin, a particularly good film can be obtained. This is preferable in terms of the water resistance, perspiration resistance, oil resistance, etc.
Among the organic silicone resins, particularly preferred is an organic silicone resin composed of the general formula R.sub.3 SiO.sub.1/2 units (wherein R is a hydrocarbon group having 1 to 6 carbon atoms or a phenyl group) and SiO.sub.2 units present in a range of a ratio of the R.sub.3 SiO.sub.1/2 units to SiO.sub.2 units of 0.5/1 to 1.5/1.
These resins are included in an amount of 2 to 60% by weight based on the total weight of the oil phase, preferably 2 to 50% by weight from the viewpoint of usability (i.e., smoothness of application), more preferably 5 to 50% by weight in view of the water resistance and oil resistance.
In the oil phase of the cosmetic composition according to the present invention, in addition to the above-mentioned oil-soluble resin, 40 to 98% by weight of a volatile oil component may be preferably formulated thereto. The volatile oil component in the oil phase may be a solvent for the resin. It is a hydrocarbon oil or silicone oil with a boiling point, at room temperature, of 60 to 260.degree. C. For example, mention may be made of Isopar (registered trademark) A, C, D, E, G, H, K, L, and M (Exxon Corp.), Sortrol (registered trademark) 100, 130, and 220 (Philips Corp.), and organic silicone oils expressed by the following general formulas (I) and (II): ##STR1## (wherein, p is an integer of from 0 to 3) ##STR2## (wherein q is an integer of from 4 to 6).
The amount of the total oil phase formulated is preferably 20 to 95% by weight, based on the total weight of the make-up cosmetic, more preferably 40 to 98% by weight.
The oil phase may further contain therein, in accordance with other objectives, within a range of amounts or quality not impairing the effect of the present invention, components generally used for cosmetics, such as solid, semisolid, or liquid oil components, pharmaceuticals, emulsifiers, thickeners, UV absorbers, clay minerals, perfumes, or other volatile components.
Next, an explanation will be made of the aqueous phase of the make-up cosmetic composition according to the present invention.
The coloring material contained in the aqueous phase may be any coloring material conventionally used for make-up cosmetics. For example, mention may be made of talc, mica, kaolin, calcium carbonate, zinc oxide, titanium dioxide, red iron oxide, yellow iron oxide, black iron oxide, ultramarine, navy blue, carbon black, lower titanium oxide, cobalt violet, chromium oxide, chromium hydroxide, cobalt titanate, bismuth oxychloride, titanium mica type pearl pigments, and other inorganic pigments, Red 201, Red 202, Red 204, Red 205, Red 220, Red 226, Red 228, Red 405, Orange 203, Yellow 205, Yellow 4, Yellow 5, Blue 1, Blue 404, Green 3, and other zirconium, barium, or aluminum lakes or other organic pigments, chlorophyll, .beta.-carotene, and other natural colors, nylon, cellulose, polyethylene, and other resin powders, dyes, etc.
Note that, for the purpose of improving the running resistance, it is preferable to use a hydrophilic coloring material so that the coloring material does not travel to the external phase, but the present invention is not limited to this, i.e., even an oleophilic coloring material may be used so long as the surface of the coloring material is made hydrophilic by a hydrophilic treatment or surfactant.
The content of these coloring materials is 0.0001 to 63% by weight in the water phase, preferably 0.1 to 50% by weight, and preferably 0.001 to 50% by weight, based upon the total weight of the make-up cosmetic composition, more preferably 0.1 to 40% by weight.
In the aqueous phase, there may preferably be mixed an emulsion resin having a film-forming ability from the viewpoint of additional usability (i.e., adhesion of film). The amount of mixture at that time is preferably 0.1 to 80% by weight of the water phase.
As the emulsion resin, mention may be made of the emulsion resins described in British Patent No. 1110240, U.S. Pat. No. 3639572, Japanese Unexamined Patent Publication (Kokai) No. 48-36347, Japanese Unexamined Patent Publication (Kokai) No. 1-203313, etc., that is, ethyl acrylate, methyl methacrylate, butyl methacrylate, methacrylic acid, vinylidene chloride and vinyl chloride copolymer emulsions, etc.
The amount of the total aqueous phase formulated is preferably 5 to 80% by weight, based upon the total weight of the make-up cosmetic composition, more preferably 20 to 60% by weight.
The water phase may also contain, in accordance with other objectives, within a range of amounts or quality not impairing the effect of the present invention, preservatives, alcohol, polyhydric alcohol, pharmaceuticals, surfactants, water-soluble polymers, thickeners, clay minerals, perfumes, antioxidants, UV absorbers, moisture retainers, etc.